Expanded olefin polymer

ABSTRACT

A thermoplastic synthetic resin such as polyethylene or ethylene-vinyl acetate copolymer resin containing 0.1 to 10 wt. % of a specific additive selected from specific classes of compounds, namely saturated higher fatty acid amides, saturated higher aliphatic amines and complete esters of saturated higher fatty acids is found to be very suitable for production of expanded articles and can be easily formed into expanded articles with little shrinkage after expansion, free from creases on the surface or cracks on the cell walls, and having excellent characteristics such as good closed cellular characteristic, high compressive strength, low density, etc.

This invention relates to a novel thermoplastic synthetic resin composition suitable for manufacturing expanded products of various kinds, which contains at least one compound selected from specific classes of compounds. This invention relates also to a process for expanding such a novel thermoplastic synthetic resin composition and to expanded products of a polyolefin resin obtained by such a process having excellent characteristics.

A thermoplastic synthetic resin of which expansion molding is difficult, for example, a polyolefin resin is known to be inferior in retentivity of gases such as of blowing agents as compared with such a resin as polystyrene resin.

Typical well-known methods of prior art for improvement of expandability of polyolefin resins may be classified broadly into four methods as follows:

(1) A method as disclosed by Japanese published examined patent applications No. 8840/1965 and No. 6278/1966, wherein the starting resin is subjected to crosslinking;

(2) A method as disclosed by U.S. Pat. No. 3,810,964, wherein the starting resin is mixed with a resin other than polyolefin resins;

(3) A method as disclosed by Japanese published examined patent applications No. 4341/1960 and No. 19628/1972, wherein there is employed a blowing agent with a composition and components specifically selected; and

(4) A method as disclosed by Japanese published examined patent applications No. 43997/1971 and No. 43998/1971, wherein there is added in the starting resin a partial ester of a specific polyhydric alcohol.

These methods, however, involve a number of drawbacks and none of them are satisfactory in commercial application. For example, according to the method (1), rheological flow properties of the resin can be improved, whereby it is possible to control resin temperature conditions optimum for melt-flow viscosity suitable for expansion. However, the temperature control range can be improved only to a small extent and besides there is no improvement of retentivity of gases such as blowing agents at all. Thus, this method fails to give substantial improvement in the art. That is, even if expansion may proceed as intended, the resultant expanded product will suffer from immediate shrinkage to be converted directly to expanded products with high density. Alternatively, even if the once shrinked expanded product may have a chance to be expanded again by the air impregnated thereinto, the creases, concavo-convex deformations on the surface or cracks on cell walls formed at the time of shrinkage cannot thereby be remedied. In consequence, no excellent expanded product can be obtained. For the same reason as mentioned above in connection with the method (1), the method (2) cannot be free from the same drawback. In addition it further involves the drawback that the desirable characteristics inherent in a polyolefin resin may be impaired. The method (3), especially that as disclosed by Japanese published examined patent application No. 4341/1960, is now accepted as the most excellent method and has been practically used for commercial production of thick expanded articles. But this method cannot also be free from the problem of shrinkage or concavo-convex deformations on the surface of the expanded products. Furthermore, the specific blowing agents to be employed in this method are too expensive to be economical. Lastly, the partial esters used in the method (4) have insufficient effect of preventing shrinkage or cannot sufficiently be kneaded with the resin, whereby expansion moldability is lowered.

An object of the present invention is to provide a resin composition which can readily be formed into an expanded product with good quality from a synthetic resin which itself is difficultly formed into an expanded product with good quality due to excessive shrinkage phenomenon, particularly a polyolefin resin composition suitable for preparation of expanded products having a bulk density of 10 to 200 kg/m³ and smooth surface, and being excellent in closed cellular structure as well as in compressive strength.

Another object of the present invention is to provide a novel expanded product of a polyolefin resin having specific characteristics of an expanded product which cannot be obtained by any of prior art methods.

Still another object of the present invention is to provide a process for expansion of a thermoplastic resin which is capable of supplying economically expanded articles with low density, high closed cell percentage having excellent surface smoothness and compressive strength by preventing shrinkage in volume of the expanded products with lapse of time.

According to the present invention, there is provided a thermoplastic resin composition for manufacturing expanded products, comprising a thermoplastic synthetic resin and at least one compound selected from the group consisting of the compounds represented by the formulas (I), (II) and (III) as set forth below contained in said resin in an amount of 0.1 to 10% by weight based on the weight of said resin: ##STR1## wherein R₁ is an alkyl group having 10 to 24 carbon atoms, X and X' each hydrogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted or a substituent containing a group of the formula --(R₄ O)_(m) -- wherein R₄ is an alkylene group having 1 to 5 carbon atoms and m an integer of 1 to 10; ##STR2## wherein R₂ is an alkyl group having 9 to 23 carbon atoms, Y and Y' each hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent containing a group of the formula --(R₄ O)_(m) -- wherein R₄ is an alkylene group having 1 to 5 carbon atoms and m an integer of 1 to 10; ##STR3## wherein [R₃ ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer 1, which may be the same or different, each having 9 to 23 carbon atoms, R₄ an alkylene group having 1 to 5 carbon atoms, k an integer of 0 to 7, l an integer of 2 to 8 and Z a l-valent residue of l-valent polyhydric alcohol from which l hydroxyl groups are eliminated.

The expanded product obtained by using the composition of the present invention as mentioned above is also novel when a polyolefin resin is used as the thermoplastic resin. Thus, the present invention also provides an expanded article of a polyolefin resin, comprising an expanded product of a polyolefin resin containing at least one compound selected from the group consisting of the compounds represented by the formulas (I), (II) and (III) as mentioned above in an amount of 0.1 to 10%by weight based on said resin and having closed cellular characteristic value of 0 to 0.5 g/cm³, a bulk density of 10 to 200 kg/m³ and a compressive strength coefficient of 2.15×10⁻³ to 2.89×10⁻².

In the accompanying drawings:

FIG. 1 shows the relationship of the volume change (ordinate) of the expanded product of the present invention (obtained in Experiment I) with lapse of time (abscissa) in which the marks , , Δ, and • correspond to Sample No. 1 to No. 5, respectively;

FIG. 2 compressive strength (at 25% compression) of several expanded products of polyethylene resin containing the additives according to the present invention and of polyethylene containing no additive plotted as ordinate versus bulk density of said products as abscissa;

FIG. 3 compressive strength (at 25% compression) of several expanded products of ethylene-vinyl acetate copolymer resin containing the additive and also of the same resin containing no additive plotted as ordinate versus bulk density of said products as abscissa (In FIG. 2 and FIG. 3 the two straight lines in the drawings correspond to critical values 2.15×10⁻³ and 2.89×10⁻², respectively);

FIG. 4 the change in volume percentage (ordinate) of expanded products (obtained in Example 10 and Comparison example 1) based on the volumes immediately after expansion with lapse of time (abscissa); and

FIG. 5 the change in weight percentage (ordinate) of expanded products (obtained in Example 10 and Comparison example 1) based on the weight immediately after expansion with lapse of time. (In FIG. 4 and FIG. 5 the marks and • correspond to Example 10 and Comparison example 1, respectively).

The specific feature of the present invention resides in use of at least one compound selected from the three classes of the compounds (I), (II) and (III) as mentioned above.

The first class of the compounds are higher alkyl amines and N-substituted derivatives thereof as represented by the above specified formula (I). The alkyl group represented by R₁ is required to have 10 to 24 carbon atoms, preferably 12 to 22 carbon atoms. It may either be straight chain, branched or alicyclic. But for the practical reason from economical standpoint such as commercial availability or cost, a straight chain alkyl having 12 to 22 carbon atoms may preferably be used. The alkyl amines (I) to be used in the present invention are inclusive of primary, secondary and tertiary amines. Thus, both of X and X' may be hydrogen atom, or one or both of them may be substituents.

Preferable examples of substituents are as follows:

    ______________________________________                                         (a)    an alkyl having 1 to 24 carbon atoms                                    (b)    (CH.sub.2).sub.nNH.sub.2 (n is an integer of 1 to 22)                   (c)                                                                                    ##STR4##                                                                 (d)  (R.sub.4 O) .sub.mH                                                       (e)                                                                                  ##STR5##                                                                 (f)                                                                                  ##STR6##                                                                 (g)                                                                                  ##STR7##                                                               ______________________________________                                    

As preferable combinations of X and X', when one of X and X' is the group (a), the other is the group (b) or (c); when one of X and X' is hydrogen atom or the group (d) or (e), the other is hydrogen atom or any of the groups (a) to (g).

Typical examples of the compounds according to the formula (I) may include dodecyl amine, tetradecyl amine, hexadecyl amine, octadecyl amine, eicosyl amine, docosyl amine, N-methyl dodecyl amine, N-methyl octadecyl amine, N-ethyl octadecyl amine, dodecyl propylene diamine, tetradecyl propylene diamine, hexadecyl propylene diamine, octadecyl propylene diamine. N-methyl hexadecyl propylene diamine, N,N'-dimethyl hexadecyl propylene diamine, N-methyl octadecyl propylene diamine, N,N'-dimethyl octadecyl propylene diamine, hexadecyl ethylene diamine, octadecyl ethylene diamine, N-methyl hexadecyl ethylene diamine, N-methyl octadecyl ethylene diamine, and the like. Typical examples of the saturated higher aliphatic amine derivatives are polyoxyethyiene myristyl amine, polyoxyethylene palmityl amine, polyoxyethylene stearyl amine, polyoxypropylene palmityl amine, polyoxypropylene stearyl amine, miristyl amine acetate, palmityl amine acetate, stearyl amine acetate, polyoxyethylene lauryl amine mono(and di-)palmitate, polyoxyethylene lauryl amine mono(and di-)stearate, .[.and.]. polyoxyethylene palmityl amine mono(and di-)palmitate, polyoxyethylene palmityl amine mono(and di-)stearate, polyoxyethylene stearyl amine mono (and di-)palmitate, polyoxyethylene stearyl amine mono(and di-)stearate, N-methyl polyoxyethylene stearyl amine palmitate, N-ethyl polyoxyethylene stearyl amine stearate, lauryl mono (and di-)ethanolamine palmitate, lauryl mono(and di-)ethanolamine stearate, palmityl mono(and di-)ethanolamine palmitate, palmityl mono(and di-)ethanolamine stearate, stearyl mono (and di-)ethanolamine palmitate, stearyl mono(and di-)ethanolamine stearate, dodecyl propylene diamine oxyethylene addition product, hexadecyl propylene diamine oxyethylene addition product, octadecyl propylene diamine oxyethylene addition product, polyoxyethylene hexadecyl propylene diamine mono(and di-)palmitate, polyoxyethylene hexadecyl propylene diamine mono(and di-)stearate, polyoxyethylene octadecyl propylene diamine mono(and di-)palmitate, polyoxyethylene octadecyl propylene diamine mono(and di-)stearate, and the like.

The second class of the compounds are saturated fatty acid amides and derivatives thereof as represented by the formula (II) as specified above. The alkyl group R₂ in the formula (II) is required to have 9 to 23 carbon atoms, preferably 11 to 21 atoms, and may be either straight chain, branched or cyclic. For the same practical reason as mentioned above in connection with R₁, R₂ may preferably a straight chain alkyl having 11 to 21 carbon atoms. Similarly, each of Y and Y' may either be hydrogen atom or a substituent. As substituents, there may be mentioned an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a group of the formula --(R₄ O)_(m) A₂ (wherein m is an integer of 1 to 10 and A₂ hydrogen atom, an alkyl having 1 to 24 carbon atoms or an acyl having 10 to 24 carbon atoms).

Typical examples of the compounds (II) are lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachic acid amide (eicosyl amide), behenic acid amide (docosyl amide), N-methyl stearic acid amide, N,N'-dimethyl stearic acid amide, di-lauric acid amide, di-palmitic acid amide, di-stearic acid amide, tri-lauric acid amide, tri-palmitic acid amide, tri-stearic acid amide, and so on. The saturated higher fatty acid amide derivatives may include lauric acid mono(and-di-)ethanolamide, myristic acid mono(and di-)ethanolamide, palmitic acid mono(and di-)ethanolamide, stearic acid mono(and di-)ethanolamide, arachic acid mono(and di-)ethanolamide, behenic acid mono(and di-)ethanolamide, lignoceric acid mono(and di-)ethanolamide, lauric acid mono-isopropanolamide, palmitic acid mono-isopropanolamide, stearic acid mono-isopropanolamide, polyoxyethylene lauric acid amide, polyoxyethylene myristic acid amide, polyoxyethylene palmitic acid amide, polyoxyethylene stearic acid amide, polyoxyethylene arachic acid amide, di-lauric acid mono-ethanolamide, di-myristic acid mono-ethanolamide, di-palmitic acid mono-ethanolamide, di-stearic acid mono-ethanolamide, di-arachic acid mono-ethanolamide, polyoxyethylene di-stearic acid amide, polyoxyethylene lauric acid amide.mono-stearate, polyoxyethylene stearic acid amide.mono-stearate, etc.

The third group of the compounds are complete esters of saturated higher fatty acids as represented by the formula (III) as specified above. They are complete esters of polyhydric alcohols of the formula Z(OH)_(l) and saturated fatty acids having 10 to 24 carbon atoms. In the above formula, the symbol [R₃ ] means plural alkyl groups comprehensively, each being attached to each ester linkage which is bonded to polyhydric alcohol residue represented by Z, and each having 9 to 23 carbon atoms. Also in this compound, straight chain alkyl having 11 to 21 carbon atoms is preferred. The complete esters may be modified by addition reaction to include polyoxyalkylene group of the formula --(OR₄)_(k) -- in the molecule. The oxyalkylene group --OR₄ -- may preferably oxyethylene or oxypropylene.

Typical examples of the compounds (III) are polyoxyethylene di-myristate, polyoxypropylene di-myristate, polyoxyethylene di-palmitate, polyoxypropylene di-palmitate, polyoxyethylene di-stearate, polyoxypropylene di-stearate, polyoxyethylene di-arachate, polyoxyethylene di-behenate, ethyleneglycol di-myristate, ethyleneglycol di-palmitate, ethyleneglycol di-stearate, ethyleneglycol di-arachate, ethyleneglycol di-behenate, lauric acid tri-glyceride, myristic acid tri-glyceride, palmitic acid tri-glyceride, stearic acid tri-glyceride, arachic acid tri-glyceride, 1,3-palmito-2-stearic acid glyceride, 1,3-stearo-2-myristic acid glyceride, sorbitane tetra-palmitate, sorbitane tetra-stearate, 12-hydroxy stearic acid tri-glyceride, sorbitane tetra-12-hydroxystearate, mono-stearic acid-di-12-hydroxystearic acid tri-glyceride, polyoxyethylene glycerine tristearate, polyoxyethylene glycerine tri-12-hydroxystearate, polyoxyethylene sorbitane tetra-stearate, polyoxyethylene sorbitane tetra-12-hydroxystearate, monostearic acid-di-12-hydroxy stearic acid polyoxyethylene tri-glyceride, and the like.

It is critically required in the present invention that at least one compound selected from the group of the compounds (I), (II) and (III) as described above should be contained in the thermoplastic synthetic resin in a total amount of 0.1 to 10% by weight based on the weight of said resin.

Referring now to Experiments I to IV set forth below, the specific behavior of the compounds within the scope of the present invention when they are contained in an amount within the range as specified above is to be described.

EXPERIMENT I

Using an ethylene-vinyl acetate copolymer (EVATATE D-2021, trade mark, produced by Sumitomo Chemical Co., Ltd.; vinyl acetate content: 10 wt. %, density: 0.93, Melt Flow Index: 1.5) as base resin, various samples are prepared by adding the compounds as shown in Table 1 and each sample is fabricated into a non-stretched sheet with thickness of about 0.15 mm.

                  TABLE 1                                                          ______________________________________                                         Additives                                                                                                  Parts per                                                                      100 parts                                          Sample           Principal  of resin                                           No.   Trade name component  (by weight)                                                                            Manufacturer                               ______________________________________                                         1     Amine A . B                                                                               Octadecyl  2       Nippon Oils &                                               amine              Fats Co., Ltd.                             2     Fatty acid Stearic    2       Kao Soap                                         amide T    acid amide/        Co., Ltd.                                                   palmitic                                                                       acid amide                                                    3     Hardened   Stearic    5       Kao Soap                                         oil        acid tri-          Co., Ltd.                                                   glyceride                                                     4     Span 85    Sorbitane  2       Kao Soap                                         (reference)                                                                               tri-oleate         Co., Ltd.                                  5     -- (Control)                                                                              --         --      --                                         ______________________________________                                    

The gas permeability characteristics of these sheets are measured according to the following method:

Device: Gas-permeability measuring instrument (LYSSY-L100-3001 model, produced by LYSSY Co.)

Gases to be permeated: Air; Dichlorotetrafluoroethane (blowing agent)

Method: Gas permeability coefficient is determined by measuring the time (seconds) needed until the inner pressure of a vessel initially maintained at 0.2 Torr at about 30° C. is increased to 0.4 Torr by the gas permeated through the sample sheet. The time is measured repeatedly until its value becomes approximately constant, and the average value of three measured values is divided by the thickness of the sheet to give the gas permeability coefficient.

The results of measurement are given in the following Table 2

                  TABLE 2                                                          ______________________________________                                                Sample No                                                                      1     2       3        4       5                                               Additive                                                                                 Fatty                                                                          acid    Har-                                                  Permeated                                                                               Amine   amide   dened  Span 85                                        gas      AB      T       oil    (reference)                                                                            Control                                ______________________________________                                         1,2-dichloro-                                                                           244     255     320    121      79                                    fluoro ethane                                                                  Air      340     350     380    490     320                                                           units sec/mm                                            ______________________________________                                    

As apparently seen from Table 2, the compositions according to the present invention (Sample Nos. 1, 2 and 3) suppress noticeably permeability of blowing agent gas as compared with Control (Sample No. 5), while they suppress little permeability of the air. On the contrary, the composition of the reference (Sample No. 4) slightly suppresses permeability of the blowing agent gas, while it greatly suppresses permeability of the air.

Based on the presumption that the well-balanced permeabilities of the air and the blowing agent gas through the resin compositions of the present invention as shown in Table 2 might be reflected in expansion procedure to result in ideal expanded products, the present inventors have made experiments to apply these compositions for manufacturing expanded products of polyethylene and ethylene-vinyl acetate copolymer resin in spite of the fact that expansion molding of polyethylene resin under uncrosslinked state has been deemed to be difficult and also that expansion molding with high closed cell percentage of ethylene-vinyl acetate copolymer resin has been substantially impossible.

The following Experiments II-IV illustrates the results of these experiments.

EXPERIMENT II

Each of the resin compositions according to Sample Nos. 1 to 5 as described in Experiment 1 is mixed with 0.1 part by weight of calcium stearate and 0.6 part by weight of calcium stearate and fed to an extruder (30 mmΦ). The mixture is kneaded internally of the extruder together with 28 parts by weight of 1,2-dichlorotetrafluoroethane and the thus mixed resin is extruded into the air while being maintained at about 90° C. to effect expansion to obtain expanded products. The density of the expanded products obtained is controlled to be 36 to 37 kg/m³.

The volume of the resultant expanded product is thereafter continued to be measured day by day. On the other hand, for the expanded product after 10 days, there are conducted measurements of compressive strength, compression permanent set, compression creep, surface smoothness, maximum shrinkage of the expanded product after expansion, dimensional stability of the expanded product and closed cellular characteristic value (each measurement method is hereinafter described).

FIG. 1 shows the relationship of the volume change with lapse of time and Table 3 the results of the measurement of various characteristics for each expanded product.

The compressive strength coefficient is also determined from the formula (2) as hereinafter described and shown in Table 3 in bracket together with 25% compressive strength (according to JIS-K-6767), since the latter varies depending on the density of the expanded product, etc.

As is clear from the above results, the composition of the present invention can be expanded using a blowing agent to give feasibly expanded products with good quality of uncrosslinked polyethylene which has hitherto been deemed to be difficult in the prior art as well as expanded products with good quality of ethylene-vinyl acetate copolymer resin which cannot practically be prepared in the prior art.

                                      TABLE 3                                      __________________________________________________________________________     Characteristics of expanded products                                           (measured after 10 days after expansion)                                                     Evaluation Items                                                 Density                                  Maximum                               [kg/m.sup.3 ] Compressive                                                                           Permanent           foam shrink-   Closed                 Items                                                                              Immediate-                                                                           After                                                                              strength                                                                              set at 50%                                                                            Compres-                                                                             Surface                                                                               age after                                                                              Dimensional                                                                           cellular               Sample                                                                             ly after                                                                             10  kg/cm.sup.2                                                                           compression                                                                           sive creep                                                                           smoothness                                                                            expansion                                                                              stability                                                                             characteristic         No. expansion                                                                            days                                                                               (coefficient)                                                                         (%)    (%)   (number/cm)                                                                           (Vol. %)                                                                               of foam                                                                               value                  __________________________________________________________________________                                                             (g/cm.sup.3)           1   36    34  1.48   10     6     0      8.0     3      0.0008                               (2.82 × 10.sup.-2)                                         2   36    34  1.46   11     6     0      5.5     5      0.0012                               (2.80 × 10.sup.-2)                                         3   36    34  1.47   11     6     0      7.5     7      0.0024                               (2.81 × 10.sup.-2)                                         4   37    64  0.10   28     24    14     51      8      0.0135                                (9.3 × 10.sup.-4)                                         5   37    51  0.11   24     21    12     35      19     0.0114                               (1.35 × 10.sup.-3)                                         __________________________________________________________________________

The concept of compressive strength coefficient is herein introduced to specify the novel expanded articles obtained by use of the composition according to the present invention. This is because apparent compressive strength as shown in Table 3 varies depending on bulk density of the expanded product and therefore it is not desirable to characterize the expanded product in terms of such an apparent compressive strength. As the result of numerous experiments, the present inventors were successful in generalization of the compressive strength relative to bulk, density according to the following formula:

    P=A×D.sup.1.248.Y

From the formula (1) is obtained:

    A=P/D.sup.1.248.Y

wherein A represents compressive strength coefficient, P 25% compressive strength measured according to JIS-K-6767, D bulk density of expanded product, the value 1.248 is the index experimentally determined from numerous data, Y is parameter (1-α/100), α being percentage (wt.) of the component to be copolymerized in the resin (for example, vinyl acetate in ethylene-vinyl acetate copolymer). This specific compressive strength coefficient is hereinafter referred to as "A value".

EXPERIMENT III

Using a low density polyethylene (Asahi-Dow Polyethylene F-1920, trade mark, produced by Asahi-Dow Limited; density: 0.919, Melt Flow Index 2.0) as base resin, the compositions 1 to 11 containing the additives and blowing agents as shown in Table 4, respectively, per 100 parts by weight of said resin are prepared by kneading similarly in an extruder and subjected to extrusion expansion as in Experiment II. As nucleators, there are employed 0.06 parts by weight of calcium stearate and 0.36 parts by weight of calcium silicate in each composition. After 10 days after formation of expanded product, 25% compressive strength is measured according to JIS-K-6767 for each expanded product from each composition to give the results as shown in FIG. 2, the numbers in FIG. 2 corresponding to those of the compositions.

EXPERIMENT IV

Using an ethylene-vinyl acetate copolymer (EVATATE K-2010, trade mark, produced by Sumitomo Chemical Co., Ltd.; vinyl acetate content 25 wt. %, density: 0.95, Melt Flow Index: 3.0) as base resin, 0.1 part of calcium stearate and 0.6 part by weight of calcium silicate as nucleators and the additives and blowing agents as shown in Table 5, under otherwise the same conditions as in Experiment III, the compositions 12 to 20 are formed into expanded products. The results of measurement conducted similarly as in Experiment III are shown in FIG. 3, wherein the numbers correspond to those of the compositions.

                  TABLE 4                                                          ______________________________________                                         Com-                                                                           po-                                                                            sition                                                                         No.   Blowing agent (wt parts)                                                                          Additive (wt parts)                                   ______________________________________                                         1     Dichlorodifluoromethane (57)                                                                      Fatty acid amide T (4.0)                              2     Dichlorodifluoromethane (57)                                                                      None                                                  3     Dichlorodifluoromethane (22)                                                                      Fatty acid amide T (2.0)                              4     Dichlorodifluoromethane (22)                                                                      None                                                  5     Dichlorodifluoromethane (5)                                                                       Amine AB (1.0)                                        6     Butane(8)          Hardened oil (3.0)                                    7     Butane(8)          None                                                  8     Butane(6)          Fatty acid amide T (0.5)                              9     Butane(6)          None                                                  10    1-chloro-1,1difluoro-                                                                             Hardened oil (2.0)                                          ethane (60)                                                              11    1-chloro-1,1-difluoro-                                                                            None                                                        ethane (60)                                                              ______________________________________                                    

                  TABLE 5                                                          ______________________________________                                         Com-                                                                           po-                                                                            sition                                                                         No.   Blowing agent (wt parts)                                                                          Additive (wt parts)                                   ______________________________________                                         12    1,2-dichloro-tetrafluoro                                                                          Amine AB (1.0)                                              ethane (10)                                                              13    Dichlorodifluoromethane (57)                                                                      Fatty acid amide T (5.0)                              14    Dichlorodifluoromethane (57)                                                                      None                                                  15    Dichlorodifluoromethane (22)                                                                      Fatty acid amide T (4.0)                              16    Dichlorodifluoromethane (22)                                                                      None                                                  17    Butane (7)         Hardened oil (2.0)                                    18    Butane (7)         None                                                  19    1-chloro-1,1-difluoro-                                                                            Hardened oil (3.0)                                          ethane (60)                                                              20    1-chloro-1,1-difluoro-                                                                            None                                                        ethane (60)                                                              ______________________________________                                    

As apparently seen from FIG. 2 and FIG. 3, the A values of the expanded products obtained by use of the compositions of the present invention are invariably within 2.15×10⁻³ to 2.89×10⁻² even when the blowing agent employed may be varied. In contrast, the A values of the expanded products using no composition of the present invention are by far smaller than the range as specified above. While being not bound by any theory, this is probably due to the following reason. Blowing agent gases contained in the expanded products are rapidly dissipated therefrom at the stage immediately after expansion in case when no composition of the present invention is employed, while the air penetrates into the expanded product considerably slowly. Consequently, at the stage before complete solidification of the resin while it is hot, the expanded product is brought internally to a state under reduced pressure, whereby it is compressed by atmospheric pressure to be shrinked. Thus, cooling is completed while giving deformations or cracks on cell walls. When the penetration of the air is slower than the cooling speed as mentioned above, the expanded product is cooled as it is to result in an expanded product with high density and having a large number of permanent creases remained on the expanded product. Even when the air may be penetrated more rapdily, simultaneously with reduction in pressure in the expanded product, to effect surface expansion of the expanded product, the deformations or cracks already formed on cell walls will prevent such surface expansion to make restoration to original volume difficult. This speculation is considered to be quite probable because the A values of the expanded products are greatly deteriorated.

Whereas, in the expanded product prepared from the composition of the present invention, the resin can be solidified with very small extent of shrinkage by permitting blowing agent gases to be replaced by the air while maintaining the ratio of both gases permeated suitably. As the result, the expanded product can be free from deformations or cracks on the cell walls to exhibit not only the excellent compressive strength coefficient but also excellent surface smoothness.

If the specific compound of the present invention is used in less than 0.1 wt. % based on the resin, no significant effect can be otained. On the contrary, an amount in excess of 10 wt. % does not necessarily lead to improvement of the effect but in some cases may cause an adverse effect on the rheological flow properties of the composition itself. Accordingly, the amount of the specific compound added is generally selected from about 0.5 to 7 wt. % from economical standpoint. There is no significant change in the amount of the compound added when it is in the composition or when it is in the expanded product, and it is calculated as a total amount of the specific compounds employed based on the weight of the resin.

For the purpose of the invention, there may be employed either a single compound or a combination of two or more compounds selected from those as mentioned above. The compound may be incorporated in the resin by any method but it is desirable to contain the compound in the resin so that said compound may be dispersed as homogeneously as possible in the resin when the composition is formed into an expanded product.

In accordance with the present invention, there is also provided a process for expanding a thermoplastic synthetic resin, which comprises incorporating at least one compound selected from the group consisting of the compounds of the formulas (I), (II) and (III) as described above in the thermoplastic synthetic resin in an amount of 0.1 to 10% by weight based on said resin together with a suitable amount of a blowing agent under the condition maintained at a temperature in the range from about 15° to 300° C. to form an expandable resin composition and then allowing said resin composition to expand utilizing the expanding force of the blowing agent contained therein.

In the process as specified above, the compounds may be incorporated in the resin by so called impregnation method wherein a substance to be incorporated is contacted with resin particles and said substance is impregnated into the resin by controlling the pressure and the temperature. Alternatively, there may also be employed so called kneading method wherein the resin and the substance to be incorporated are subjected to mixing and kneading. Furthermore, a combination of both methods may also be applicable. The substances to be incorporated may either be simultaneous or stepwise. These operations may be conducted under well known conditions, namely at a temperature in the range from 15° to 300° C. and a pressure of 0.05 to 300 kg/cm² (gauge).

The expanding force of blowing agent used in this process is obtained through phase transfer (from liquid phase to gas phase), volume expansion of blowing agent and decomposition of blowing agent (from solid to gas), and therefore the conditions are determined depending on the blowing agent employed and expanding operations. For example, when a physical blowing agent is used in extrusion expansion, a resin kneaded for temperature adjustment at a temperature of about 60° to 280° C. under a pressure of 5 to 200 kg/cm² can be extruded into the atmosphere at a temperature of about 20° C. and under pressure of 1 atm. to obtain sufficient expanding force. Alternatively, when a physical blowing agent is used in cavity expansion, a resin containing a blowing agent is filled in a cavity and the cavity is heated under conditions at a temperature of about 115° C. under pressure of 0.23 kg/cm² (gauge).

The specific feature of the process according to the present invention resides in allowing a thermoplastic synthetic resin composition containing 0.1 to 10 wt. % of at least one compound as specified by the formulas (I), (II) and (III) to expand with a blowing agent which is also contained in said resin. This is because, in the absence of the specific compound, the expanded product suffers from shrinkage in the course of preparation and with lapse of time, as explained with reference to FIGS. 1 to 3 and Table 3, thereby giving only expanded products with high density, having much concavo-convex deformations or creases or being very low in closed cell percentage. In particular, no expanded product with excellent compressive strength can be obtained in the absence of the specific compound.

Similarly as described in connection with the composition of the present invention, an amount of the specific compound less than 0.1 wt. % fails to give the effect of the invention, while an amount exceeding 10 wt. % may cause adverse effect rather than better results. The specific compounds may also be used either singly or in a mixture of two or more compounds. The preferable total amount of the specific compounds falls also within 0.5 to 7 wt. %. They can be contained in the resin in any conventional manner, but it is desirable to disperse the compounds as homogeneously as possible throughout the entire resin.

As blowing agents to be used in the present invention, volatile organic blowing agents and thermally decomposable gas-releasing chemical blowing agents are available. Preferably, there may be employed volatile organic blowing agents having boiling point (at 1 atm.) not higher than melting point of the base resin, such as trichlorofluoromethane, dichlorodifluoromethane, dichlorofluoromethane, chlorodifluoromethane, 1,1',2-trichlorotrifluoroethane, 1,2-dichlorotetrafluoroethane, 1-chlorotrifluoroethane, 1-chloro-1,1'-difluoroethane, 1,1'-difluoroethane, octafluorodichlorobutane, propane, butane, butene, propylene, pentane, etc. When the base resin to be expanded is a non-crosslinked polyolefin resin, it is preferred to select a volatile blowing agent from those as enumerated above having a Kauri-Butanol value in the range of 10 to 25 as determined by the method according to ASTM-D-1133-61.

These blowing agents may be employed generally in an amount in the range from 5 to 70% by weight based on the resin depending on the desired density of expanded products.

The process of the present invention is expected to be most advantageously be applied in the field of so called continuous extrusion expansion. In this case, for example, the base resin, the specific compound and blowing agent are fed into an extruder heated at a temperature higher than melting point of the base resin (generally about 120° to 280° C.), kneaded under a pressure generally of about 50 to 300 kg/cm² therein, then said mixture is adjusted to a temperature suitable for expansion in the range from the melting point of the base resin to the temperature lower by 50° C. than the melting point (generally about 60° to 200° C.) before being extruded through an orifice to the outside at about 25° C. under atmospheric pressure, thereby accomplishing expansion simultaneously with extrusion, followed by cooling to produce expanded articles. This technique is economical in continuous expansion of a large amount of resins. In particular, by use of the specific compound of the present invention, it is rendered possible to select a blowing agent from a large number of less expensive compounds which have hitherto been insufficient in expandability when used alone as blowing agents. To speak one typical example, in place of an expensive blowing agent 1,2-dichlorotetrafluoroethane, there can be employed less expensive blowing agents such as dichlorodifluoromethane, propane or butane to a great economical advantage.

The thermoplastic synthetic resin to be used in the present invention refer to all polymers, copolymers and mixed polymers which can be subjected to melt fabrication. In particular, thermoplastic synthetic resins which can be improved in expandability by addition of the specific compound of the present invention are those which will undergo shrinkage when expanded due to the greater ratio S'/S exceeding 1 of permeating speed (S') of volatile hydrocarbon or fluorocarbon gas through said resin film to that (S) of the air (at the time of expansion as estimated by FIG. 4 and FIG. 5). More specifically, they may include crosslinked or non-crosslinked polyolefin resins such as ethylene homopolymers (e.g. high density polyethylene, medium density polyethylene or low density polyethylene or a mixture thereof), ethylenic copolymers having ethylene content of 50% or more (e.g. ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, a metallic salt of an ethylene-acrylic acid copolymer, ethylene-propylene copolymer, ethylene-vinyl chloride copolymer), polypropylene and polybutene-1. Among them, polyethylene resin and ethylene-vinyl acetate copolymer are preferably used. The polyolefin resin to be employed in the present invention may have a melt index which is not specifically limited but generally within the range from 0.3 to 45. When it is desired to employ a crosslinked polyolefin resin, it may be prepared by conventional method by effecting crosslinking using a crosslinking agent such as organic peroxides or irradiation of electron beam.

The resin composition of the present invention may further contain, if desired, other inorganic or organic additives such as pigments, fire-retardants, lubricants, anti-oxidants, UV-absorbers, nucleators, anti-static agents or others in an amount of preferably no more than 3% by weight based on the weight of the resin. In particular, it is preferable to use a small amount (not more than 1% by weight) of nucleators such as talc or a fatty acid metal salt in order to control uniformly the cell distribution in the resultant expanded product.

The present invention is further illustrated with reference to the following Examples and Comparison Examples. The measurement of characteristic values and evaluation of these values herein mentioned are conducted by the methods and the criteria, respectively, as set forth below.

1. Compressive strength and compressive strength coefficient

(a) 25% compressive strength (P):

Compressive strength at the time of 25% compression is measured according to JIS-K=6767.

(b) compressive strength coefficient (A):

This value is calculated by the formula (2) as mentioned above from the above compressive strength (P) and bulk density (D) of expanded product.

2. 50% compression permanent set:

According to JIS-K-6767 (at the time of 50% compression).

3. Compression creep:

According to JIS-K-6767 (under area load of 0.1 Kg/cm² ·24 hour)

4. Surface smoothness:

The surface of expanded product is measured over 10 cm length by coarseness measuring instrument to detect creases or concavo-convexes with width of 0.5 mm or more and the number detected is calculated per 1 cm length.

5. Feeding characteristic through extruder:

Change in amount extruded per one minute when performing extrusion by 30 mmΦ extruder is expressed by variance percentage (n=15). ##EQU1## 6. Maximum shrinkage: Volume of expanded product is masured (by watersink method) every day for 20 days after expansion and maximum shrinkage is calculated by the following formula: ##EQU2## 7. Dimensional stability: From the result of measurement 6. as mentioned above, dimensional stability is calculated by the following formula: ##EQU3## (wherein V₀ is volume of expanded product immediately after expansion and V₂₀ that after 20 days.)

8. Closed cellular characteristic value:

In water in a vessel having water volume sufficient to sink sample in water and a function to be sealed is sunk an expanded product sample of 15 mm×15 mm×100 mm (volume: V; weight: W₀) to be held therein, followed by sealing of the vessel. Subsequently, the inner pressure in the vessel is reduced to 460 mm Hg and left to stand for 10 minutes. Then, the inner pressure in the vessel is restored to atmospheric and the sample is taken out. The sample is calmly dipped in pure methanol for about 2 seconds, followed by wipe-off of the moisture adhered on the surface, dried in a drier at 60° C. for 5 minutes and thereafter its weight (W₁) is measured. Closed cellular characteristic value is calculated by the following formula: ##EQU4## 9. Criteria for evaluation: Each evaluation item is rated according to the ranks as shown in the following Table:

    ______________________________________                                                  Ranks                                                                 Evaluation a         b         c       d                                       item       (excellent)                                                                              (good)    (passable)                                                                             (bad)                                   ______________________________________                                         1.  Compressive                                                                               8.0 × 10.sup.-3                                                                    4.0 × 10.sup.-3                                                                  2.15× 10.sup.-3                                                                  less                                      strength   or more   or more,                                                                               or more,                                                                               than                                      coefficient          less than                                                                              less than                                                                              2.15 ×                                                   8.0 × 10.sup.-3                                                                  4.0 × 10.sup.-3                                                                  10.sup.-3                             2.  50%        less than 5 or more                                                                              15 or more                                                                             30 or                                     compression                                                                               5 to 0    less than 15                                                                           less than 30                                                                           more                                      permanent                                                                      wt (%)                                                                     3.  Compressive                                                                               less than 5 or more,                                                                             10 or more,                                                                            20 or                                     creep (%)  5 to 0    less than 10                                                                           less than 20                                                                           more                                  4.  Surface    less than 3 or more,                                                                             6 or more,                                                                             10 or                                     smoothness 3 to 0    less than 6                                                                            less than 10                                                                           more                                      (number/cm)                                                                5.  Feeding    less than 5 or more,                                                                             10 or more,                                                                            15 or                                     character- 5 to 0    less than 10                                                                           less than 15                                                                           more                                      istic of                                                                       extruder (%)                                                               6.  Maximum    less than 10 or more,                                                                            15 or more,                                                                            20 or                                     shrinkage  10 to 0   less than 15                                                                           less than 20                                                                           more                                      (%)                                                                        7.  Dimensional                                                                               less than 5 or more,                                                                             10 or more,                                                                            15 or                                     stability  5 to 0    less than 10                                                                           less than 15                                                                           more                                      (%)                                                                        8.  Closed     less than 0.010 or                                                                               0.025 or                                                                               0.50 or                                   cellular   0010 to 0 more, less                                                                             more, less                                                                             more                                      characteristic       than 0.025                                                                             than 0.50                                         (g/cm.sup.3)                                                               ______________________________________                                    

Overall evaluation is rated from the ranks as set forth above according to the following ranks:

    ______________________________________                                         a (excellent)                                                                               when there are at least two excellent                                          marks with no bad or passable mark                                b (good)     when there is at least one good mark                                           with no bad mark and not more than                                             two passable marks                                                c (passable) when there are three or more passable                                          marks with no bad mark                                            d (bad)      when there is one or more bad mark                                ______________________________________                                    

The details of the thermoplastic synthetic resins and the specific compounds employed in the following Examples and Comparison Examples are listed below.

Thermoplastic resins:

Resin A: low density polyethylene produced by Asahi-Dow Limited, F-1920, trade mark, density: 0.919 g/cc, MI: 2.0 g/10 min.

Resin B: ethylene-vinyl acetate copolymer produced by Sumitomo Chemical Co., Ltd., EVATATE D-2021, trade mark, vinyl acetate content: 10 wt. %, density: 0.93 g/cc, MI: 1.5 g/10 min.

Resin C: ethylene-vinyl acetate copolymer produced by Sumitomo Chemical Co., Ltd., EVATATE K-2010, trade mark, vinyl acetate content: 25 wt. %, density: 0.95 g/cc, MI: 3.0 g/10 min.

Additives (Nos. 1-18: specific compounds of the invention; Nos. 19-31: reference compounds)

    ______________________________________                                              Trade name of           Name of                                           No.  additives   Manufacturer                                                                               the compounds                                     ______________________________________                                         1    Fatty acid  Kao Soap Co.,                                                                              Stearic acid amide and                                 amide T     Ltd.        palmitic acid amide                                                            (mixture)                                         2    Amine BB    Nippon Oils &                                                                              Dodecyl amine                                                      Fats Co., Ltd.                                                3    Amine AB    Nippon Oils &                                                                              Octadecyl amine                                                    Fats Co. Ltd.                                                 4    N--methyl-  Nippon Oils &                                                                              N--methyloctadecyl                                     octadecyl   Fats Co., Ltd.                                                                             amine                                                  amine                                                                     5    Asfazol #20 Nippon Oils &                                                                              Stearyl propylene                                                  Fats Co., Ltd.                                                                             diamine                                           6    Naimine S-202                                                                              Kao Soap Co.,                                                                              Polyoxyethylene octa-                                              Ltd.        decyl amine (2 moles                                                           of oxyethylene added)                             7    Naimine S-210                                                                              Kao Soap Co.,                                                                              Polyoxyethylene octa-                                              Ltd.        decyl amine (10 moles                                                          of oxyethylene added)                             8    Denon 331 P Marubishi   Polyoxyethylene stearyl                                            Petrochemical                                                                              amine mono- and di-                                                Co.         stearate (mixture)                                9    Esodaomine  Lion Fat &  Polyoxyethylene stearyl                                T-13        Oil Co., Ltd.                                                                              and palmityl diamine                                                           (mixture: 3 moles of                                                           oxyethylene added)                                10   Resicoat 1936                                                                              Lion Fat &  Oxyethylene stearyl and                                            Oil Co., Ltd.                                                                              palmoctyl diamine                                                              (mixture: one mole of                                                          oxyethylene added)                                11   Fatty acid  Kao Soap Co.,                                                                              Lauric acid amide                                      amide C     Ltd.                                                          12   Amazol SDE  Kawaken Fine                                                                               1:1-type stearic acid                                              Chemical Co.,                                                                              dictbanolamide                                                     Ltd.                                                          13   Amazol SME  Kawaken Fine                                                                               1:1-type stearic acid                                              Chemical Co.,                                                                              mono-ethanolamide                                                  Ltd.                                                          14   Amozol LME  Kawaken Fine                                                                               1:1-lauric acid                                                    Chemical Co.,                                                                              mono-ethanolamide                                                  Ltd.                                                          15   Fatty acid  Kao Soap Co.,                                                                              Palmitic acid amide                                    amide P     Ltd.                                                          16   Hardened oil                                                                               Kao Soap Co.,                                                                              Stearic acid triglyceride                                          Ltd.                                                          17   Koa wax 85  Koa Soap Co.,                                                                              12-hydroxy stearic acid                                powder      Ltd.        triglyceride                                      18   Unister-E-275                                                                              Nippon Oils &                                                                              Ethyleneglycol                                                     Fats Co., Ltd.                                                                             distearate                                        19   Syntolex    Nippon Oils &                                                                              Sodium lauryl sulfate                                  L-100       Fats Co., Ltd.                                                20   A.mos-150   Kao Soap Co.,                                                                              Stearic acid mono- and                                             Ltd.        di-glyceride                                      21   Cation      Nippon Oils &                                                                              Octadecyl dimethyl-                                    S.sub.2 -100                                                                               Fats Co., Ltd.                                                                             benzyl ammonium                                                                chloride                                          22   Noion       Nippon Oils &                                                                              Polyoxyethylene                                        SN-204.5    Fats Co., Ltd.                                                                             nonyl phenol ether                                23   Caproic     Kanto Chemical                                                                             Caproic acid amide                                     acid amide  Co., Ltd.                                                     24   Span 85     Kao Soap Co.,                                                                              Sorbitane trioleate                                                Ltd.                                                          25   Triphenyl   Kanto Chemical                                                                             Triphenyl carbinol                                     carbinol    Co., Ltd.                                                     26   1,2-diphenyl                                                                               Kanto Chemical                                                                             1,2-diphenyl ethylene-                                 ethylene-   Co., Ltd.   diamine                                                diamine                                                                   27   Phthalamide Kanto Chemical                                                                             Phthalamide                                                        Co., Ltd.                                                     28   Lunac S-30  Kao Soap Co.,                                                                              Stearic acid                                                       Ltd.                                                          29   Zinc stearate                                                                              Sakai       Zinc stearate                                                      Chemical Co.,                                                                  Ltd.                                                          30   Fatty acid  Kao Soap Co.,                                                                              Oleic acid amide                                       amide O     Ltd.                                                          31   Alfro P-10  Nippon Oils &                                                                              Erucic amide                                                       Fats Co., Ltd,                                                ______________________________________                                    

EXAMPLES 1-18 AND COMPARISON EXAMPLES 1-14

To 100 parts by weight of Resin B are added various additives as shown in Table 6, 0.1 part by weight of calcium stearate, 0.6 part by weight of calcium silicate and 22 parts by weight of a volatile blowing agent dichlorodifluormethane. Each mixture is kneaded by means of a 30 mm single screw extruder equipped with a round orifice of 5 mm in diameter and heated at 190° C. By adjusting the resin temperature in the orifice at 90° C., extrusion expansion is carried out for each mixture to prepare an expanded product thereof. These expanded products are subjected to evaluation test as described above to give the results as shown in Table 6. Table 6 clearly shows that the expanded products of Examples 1 to 18 containing the compounds of the formulas (I) to (III) exhibit superior values to those of Comparison example 1 containing no additive and Comparison examples 2 to 14 containing other compounds than those of the formulas (I) to (III).

The volumes and weights of the expanded products obtained in Example 10 and Comparison example 1 are continued to be measured every day for about one month, respectively, and the percentages of volumes and the weights based on those immediately after expansion are plotted versus lapse of time (days) in FIG. 4 and FIG. 5.

As apparently seen from FIG. 4 and FIG. 5, the expanded product of Example 10 is reduced in weight with lapse of time, while its volume is not reduced with small shrinkage and good restorability. In contrast, the expanded product of Comparison example 1 suffers from abrupt and noticeable shrinkage with reduction in weight and its volume restored with lapse of time is at most about 60%.

    TABLE 6       Base resin:  B, 100 wt. parts Nucleators: Calcium stearate 0.1 wt.      part, calcium silicate 0.6 wt. part Blowing agent: Dichlorodifluoromethan      e 22 wt. parts .Iadd.Evaluation.Iaddend. Density     Feeding   Closed      (10 days after Compressive 50%   characteristic  Dimensional cellular      expansion) strength compression Compression Surface through Maximum      .[.stabiity.]. characteristic Overall g/cm.sup.3 coefficient permanent      set creep smoothness extruder shrinkage stability value evaluation        Additives wt. parts   Type of            Example compounds Trade name      1  Amine BB (2.0) 0.029 a b b a a a a a a 2  Amine AB (2.0) " a b b a a      a a a a 3 Saturated N--methyl- 0.030 a b b a a a a a a  higher octadecyl       aliphatic amine (2.0) 4 amine Asfazol #20 " a b b a b a a a a  compounds       (2.0) 5  Naimine S-202 0.029 a b b b b b a a a   (2.0) 6  Naimine S-210      " a b b b b b a a a   (2.0) 7  Denon 331P 0.030 a b b b b b a a a      (5.0) 8  Esoduomine F13 " a b b a b a a a a   (3.0) 9  Resicoat 1936 " a      b b a b a a a a   (3.0) 10  Fatty acid 0.029 a b b a a a a a a   amide T      (1.0) 11 Saturated Fatty acid " a b b a a a a a a  higher amide C (3.0)      12 fatty Amizol SDE " a b b a a a a a a  acid (2.0) 13 amides Amizol SME      0.030 a b b a a a a a a   (2.0) 14  Amizol LME " a b b a a a a a a      (2.0) 15  Fatty acid 0.029 a b b a a a a a a   amide P (2.0) 16 Complete      Hardened " a b b a b a a a a  esters oil (1.5) 17 of  " a b b a b a a a      a  saturated Kao wax 85  higher powder (1.5) 18 fatty Unister E275 0.030      a b b b b b a a a  acids (1.5)        Comparison Additive           example trade name (wt. parts) 1 None      0.075 d d d d a d d b d 2 Atmos 150 (1.5) " c c c d d c d b d 3 Syntolex      L-100 (2.0) " d d d d b d d b d 4 Cation S.sub.2 -100 (2.0) 0.073 d d d      d b d d b d 5 Nonion NS 204.5 (2.0) 0.072 d d d d d d d b d 6 Capronamide       (2.0) " d d d d a d d b d 7 Fatty acid amide O (2.0) 0.074 d d d d b d      d b d 8 Alfro P-10 (2.0) 0.074 d d d d b d d b d 9 Span 85 (2.0) " d d d      d d d d b 10 Triphenyl carbinoyl (2.0) " d d d d b d d b d 11 1,2-Dipheny      l 0.073 d d d d b d d b d  ethylenediamine (2.0) 12 Phthalamide (2.0)      0.075 d d d d b d d b d 13 Lunac 5-30 (2.0) " d d d d b d d b d 14 Zinc      stearate 2.0 " d d d d b d d b d

EXAMPLES .Badd.19-27 AND COMPARISON EXAMPLES 15-17

Expanded products are prepared similarly as described in Examples 1-18 except that 100 parts by weight of Resin A are used as base resin, 0.06 parts by weight of calcium stearate and 0.36 part by weight of calcium silicate powders as nucleators and the blowing agents D, E and F as shown in Table 7 in amounts of 22, 20 and 8 parts by weight, respectively, and that the resin temperature in the orifice is controlled at 104° C. From the results shown in Table 7, it is clearly seen that Examples 19 to 27 give better results than Comparison Examples 15 to 17 when various blowing agents D, E and F are employed.

                                      TABLE 7                                      __________________________________________________________________________              Base resin:                                                                            A 100 wt. parts                                                        Nucleators:                                                                            Calcium stearate 0.06 wt. parts, calcium silicate 0.36                         wt. parts                                                              Blowing agents:                                                                        D: Dichlorodifluoromethane                                                                    22 wt. parts                                                    E: 1-chloro-1,1-difluoroethane                                                                20 wt. parts                                                    F: Butane       8 wt. parts                                   __________________________________________________________________________                                  Density                                                                               Evaluation                                                              (10 days after                                                                        Compressive                                                                          50%                                                          Blowing                                                                             expansion                                                                             strength                                                                             compression                                                                           Compression                                                                           Surface                                        agent                                                                               g/cm.sup.3                                                                            coefficient                                                                          permanent set                                                                         creep  smoothness             __________________________________________________________________________             Additive (wt. parts)                                                           Type of                                                                Example compounds                                                                             Trade name                                                      19      Saturated                                                                             Amine AB (1.0)                                                                          D    0.030  a     a      a      a                      20      higher Amine AB (3.0)                                                                          E    0.032  a     b      b      b                      21      aliphatic                                                                             Amine AB (7.0)                                                                          F    0.034  a     b      b      b                              amines                                                                 22      Saturated                                                                             Fatty acid                                                                              D    0.030  a     a      a      a                              higher amide T (0.3)                                                   23      fatty  Fatty acid                                                                              E    0.032  a     b      a      a                              acid   amide T (2.0)                                                   24      amides Fatty acid                                                                              F    0.033  a     b      b      b                                     amide T (5.0)                                                   25      Complete                                                                              Hardened D    0.030  a     a      a      a                              esters of                                                                             oil (4.0)                                                       26      saturated                                                                             Hardened E    0.033  a     b      b      b                              higher oil (6.0)                                                       27      fatty  Hardened F    0.034  a     b      b      b                              acids  oil (10.0)                                                      __________________________________________________________________________     Comparison                                                                     example Additives                                                              15      None            D    0.063  d     d      d      d                      16      None            E    0.062  d     d      d      d                      17      None            F    0.069  d     d      d      d                      __________________________________________________________________________                                   Evaluation                                                                     Feeding             Closed                                                     characteristic      cellular                                                   through                                                                               Maximum                                                                              Dimensional                                                                           characteristic                                                                        Overall                                             extruder                                                                              shrinkage                                                                            stability                                                                             value  evaluation            __________________________________________________________________________                   Additives (wt. parts)                                                          Type of                                                          Example       compounds                                                                             Trade name                                                19            Saturated                                                                             Amine AB (1.0)                                                                          a      a     a      a      a                     20            higher Amine AB (3.0)                                                                          a      b     a      a      a                     21            aliphatic                                                                             Amine AB (2.0)                                                                          b      b     a      a      a                                   amines                                                           22            Saturated                                                                             Fatty acid                                                                              a      a     a      a      a                                   higher amide T (0.3)                                             23            fatty  Fatty acid                                                                              a      b     a      a      a                                   acid   amide T (2.0)                                             24            amides Fatty acid                                                                              b      b     a      a      a                                          amide T (5.0)                                             25            Complete                                                                              Hardened b      a     a      a      a                                   esters of                                                                             oil (4.0)                                                 26            saturated                                                                             Hardened b      b     a      a      a                                   higher oil (6.0)                                                 27            fatty  Hardened b      b     a      a      a                                   acids  oil (10.0)                                                __________________________________________________________________________     Comparison                                                                     example       Additives                                                        15            None            a      d     d      b      d                     16            None            a      d     d      b      d                     17            None            a      d     d      b      d                     __________________________________________________________________________

EXAMPLES 28-36 AND COMPARISON EXAMPLES 18-21

Using 100 parts by weight of Resin C as base resin, blowing agents D, E, G and H as shown in Table 8 in amounts of 22, 20, 28 and 26 parts by weight, respectively, and the additives as shown in Table 8 in amounts indicated therein, and also adjusting the resin temperature in the orifice at 78° C., under otherwise the same conditions as described in Examples 1 to 18, various expanded products are prepared. The results are shown in Table 5, which clearly shows that Examples 28 to 36 give better results than Comparison examples 18 to 21 even when there is employed Resin C of an ethylene-vinyl acetate copolymer with higher vinyl acetate content from which a volatile blowing agent is liable to be readily escaped.

                                      TABLE 8                                      __________________________________________________________________________              Base resin:                                                                            C 100 wt. parts                                                        Nucleators:                                                                            Calcium stearate 0.1 wt. parts, calcium silicate 0.6 wt.                       parts                                                                  Blowing agents:                                                                        D: Dichlorodifluoromethane                                                                    22 wt. parts                                                    .[.E: 1-chloro-1,1-difluorethane.].                                                           20 .Iadd.wt. .Iaddend.parts                                     .Iadd.E: 1-chloro-1,1-difluoroethane.Iaddend.                                  G: 1,2-dichlorotetrafluoroethane                                                              28 wt. parts                                                    H: 1,2-dichlorotetrafluoroethane/mono-chloropentafluoroet                      hane =                          75/25 (wt. ratio)                                                              26 wt.                        __________________________________________________________________________                                                      parts                                                 .[.Blow-.]. Evaluation                                                         .[.ing.].                                                                           Density                     .[.Feeding.].                                 .[.agent.].                                                                         (10 days after                                                                        Compressive                                                                          50%           .[.character-.].                               Blowing                                                                             expansion                                                                             strength                                                                             compression                                                                           Compression                                                                           Surface                                        agents                                                                              g/cm/hu 3                                                                             coefficient                                                                          permanent set                                                                         creep  smoothness             __________________________________________________________________________             Additive (wt. parts)                                                           Type of                                                                Example compounds                                                                             Trade name                                                      28      Saturated                                                                             Amine AB (3.0)                                                                          D    0.031  a     b      b      a                      29      higher Amine AB (5.0)                                                                          E    0.033  a     b      b      a                      30      aliphatic                                                                             Amine AB (2.0)                                                          amine                                                                  31      Saturated                                                                             Fatty acid                                                                              G    0.037  a     b      b      a                              higher amide T (2.0)                                                                           D    0.030  a     b      b      a                      32      fatty  Fatty acid                                                                              E    0.032  a     b      b      a                              acid   amide T (3.0)                                                   33      amine  Fatty acid                                                                              G    0.038  a     b      b      a                                     amide T (1.0)                                                   34      Complete                                                                              Hardened D    0.030  b     b      b      a                              ester of                                                                              oil (5.0)                                                       35      saturated                                                                             Hardened E    0.033  b     b      b      b                              higher oil (8.0)                                                       36      fatty  Hardened G    0.038  b     b      b      b                              acid   oil (3.0)                                                       __________________________________________________________________________     Comparison                                                                     example Additives                                                              18      None            D    0.084  d     d      d      d                      19      None            E    0.084  d     d      d      d                      20      None            G    0.064  d     d      d      d                      21      None            H    0.032  c     c      c      b                      __________________________________________________________________________                                   Evaluation                                                                     .Iadd.Feeding.Iaddend.                                                                             Closed                                                     .Iadd.characteristc.Iaddend.                                                                       cellular                                                   through                                                                               Maximum                                                                              Dimensional                                                                           characteristic                                                                        Overall                                             extruder                                                                              shrinkage                                                                            stability                                                                             value  evaluation            __________________________________________________________________________                   Additives (wt. parts)                                                          Type of                                                          Example       compounds                                                                             Trade name                                                28            Saturated                                                                             Amine AB (3.0)                                                                          a      a     a      a      a                     29            higher Amine AB (5.0)                                                                          b      a     a      b      a                     30            aliphatic                                                                             Amine AB (2.0)                                                          amine                                                            31            Saturated                                                                             Fatty acid                                                                              a      a     a      a      a                                   higher amide T (2.0)                                                                           a      a     a      a      a                     32            fatty  Fatty acid                                                                              a      a     a      a      a                                   acid   amide T (3.0)                                             33            amine  Fatty acid                                                                              a      a     a      a      a                                          amide T (1.0)                                             34            Complete                                                                              Hardened b      a     a      a      a                                   ester of                                                                              oil (5.0)                                                 35            saturated                                                                             Hardened b      a     a      b      a                                   higher oil (8.0)                                                 36            fatty  Hardened b      a     a      a      a                                   acid   oil (3.0)                                                 __________________________________________________________________________     Comparison                                                                     example       Additives                                                        18            None            a      d     d      b      d                     19            None            a      d     d      b      d                     20            None            a      d     d      b      d                     21            None            a      b     b      d      d                     __________________________________________________________________________

EXAMPLES 37-39 AND COMPARISON EXAMPLES 22-24

According to the same procedure as in Examples 1-18 except for the specific compounds and their amounts and the amounts of dichlorodifluoromethane as shown in Table 9, various expanded products are prepared. The results as shown in Table 9 indicate that the products of Examples 37-39 are better in expansion moldability and physical properties of the resultant expanded products than those of the Comparative examples even when the amounts of the blowing agent are greatly changed as shown in Table 9.

                                      TABLE 9                                      __________________________________________________________________________                  Resin:  B 100 wt. parts                                                        Nucleators:                                                                            Calcium stearate 0.1 wt. parts, calcium silicate 0.6                           wt. part                                                               Blowing agent:                                                                         Dichlorodifluoromethane                                                        Evaluation                                                                Density    50%           Feeding      Closed                             Amount                                                                               (10 days                                                                            Com-  com- Com-     charac-                                                                             Maxi-   cellular                                                                            Over-               Additives .Iadd.of .Iaddend.blow-                                                              after ex-                                                                           pressive                                                                             pression                                                                            pres-                                                                              Surface                                                                             teristic                                                                            mum Dimen-                                                                             charac-                                                                             all                 trade name                                                                               ing agent                                                                            pansion)                                                                            strength                                                                             perma-                                                                              sion                                                                               smooth-                                                                             through                                                                             shrink-                                                                            sional                                                                             teristic                                                                            evalu-              (wt. parts)                                                                              (wt. parts)                                                                          g/cm.sup.3                                                                          coefficient                                                                          nent set                                                                            creep                                                                              ness extruder                                                                            age stability                                                                          value                                                                               ation               __________________________________________________________________________     Example                                                                        37  Fatty acid                                                                           60    0.014                                                                               a     b    b   a    b    a   a         a                      amide T (4)                                                                38  Fatty acid                                                                           9     0.077                                                                               a     b    b   a    a    a   a   a    a                       amide T (2)                                                                39  Fatty acid                                                                           5     0.174                                                                               a     a    a   a    a    a   a   a    a                       amide T (1)                                                                Comparison                                                                                .[.60.].                                                            example                                                                        22        .Iadd.60.Iaddend.                                                                    0.080                                                                               d     d    d   d    a    d   d   b    d                   23        9     0.089                                                                               c     c    d   d    a    d   b   b    d                   24        5     0.195                                                                               b     c    c   c    a    d   c   d    d                   __________________________________________________________________________

EXAMPLE 40

In polyethylene resin (F-2130, trade mark, produced by Asahi-Dow Limited, density: 0.921 g/cc, MI: 3.0 g/10 min.), there are added by kneading 0.45% by weight of dicumyl peroxide as crosslinking agent and 1.5% by weight of stearic acid amide (Fatty acid amide T, trade mark, produced by Kao Soap Co., Ltd.) and the mixture is subjected to crosslinking reaction. The resultant crosslinked polyethylene resin particles (spherical with diameter of 1.5 mm) with gel content of 61% are impregnated in an autoclave with dichlorodifluoromethane under pressurization with heating and thereafter cooled. The expandable crosslinked polyethylene resin particles thus obtained are found to contain 14 wt. % of dichlorodifluoromethane. These particles are placed in a pressure-type expanding vessel wherein they are allowed to expand while passing steam of 0.23 Kg/cm² ·G for 45 seconds to obtain primarily expanded particles with density of 100 Kg/m³. Subsequently, these primarily expanded particles are placed in an autoclave and, under pressurization with the air at 10 Kg/cm² ·G, heat treatment is conducted at 80° C. for 15 hours to increase inner pressure in the cells, followed by passing of steam of 0.32 Kg/cm² to effect expansion to obtain secondarily expanded particles with density of 27 Kg/m³. After increasing the inner pressure in the cells of these secondarily expanded particles, they are filled under compression in a cavity in a molding machine (ECHO-120 model, produced by Toyo Machinery & Metal Co., Ltd.) and subjected to expansion fusion molding by heating with steam of 1.1 Kg/cm² ·G. The density of the molded expanded product is found to be 25 Kg/m³ and have a closed cellular characteristic value of less than 0.01.

COMPARISON EXAMPLE 25

Example 40 is repeated except that no stearic acid amide is added. The resultant primarily expanded particles are found to have a density of 111 Kg/m³, while the secondarily expanded articles a density of 31 Kg/m³. The expanded particles have higher density as compared with those of Example 40 and said particles are found to have relatively large number of creases. When the secondarily expanded particles are molded similarly as in Example 40, the expanded product obtained is found to have a density of 30 Kg/m³. It is also inferior in closed cell percentage and compressive strength to that of Example 40. The life of beads impregnated with blowing agent for retaining desirable expandability is also shorter by one hour as compared with those of Example 40.

EXAMPLE 41

Using a mixed resin comprising 60 parts by weight of a high density polyethylene (Suntec S-360, trade mark, produced by Asahi Kasei Kogyo Kabushiki Kaisha, density: 0.950 g/cc) and 40 parts by weight of an ionomer (Surlyn A 1706, trade mark, produced by E. I. du Pont de Nemours, Inc.), 1.5 parts by weight of stearic acid amide as specific additive (Fatty acid amide T, trade mark, produced by Kao Soap Co., Ltd.), 0.3 part by weight of calcium silicate powders as nucleators and 27 parts by weight of dichlorodifluoromethane as volatile blowing agent are kneaded with said mixed resin in a 30 mm single screw extruder equipped with an orifice with diameter of 5 mm and heated at 220° C. While adjusting the resin temperature in the orifice at 122° C., extrusion expansion is conducted to obtain expanded product having excellent characteristics such as closed cellular characteristic of 0.005 g/cm³, density of 23 Kg/m³, compressive strength coefficient of 2.01×10⁻² and maximum expansion shrinkage of 0.2%.

EXAMPLE 42

Example 41 is repeated except that the base resin of high density polyethylene is replaced by isotactic polypropylene (Chisso Polypro 1011, trade mark, produced by Chisso Corporation) and the resin temperature in the orifice is adjusted at 135° C. The expanded product obtained is found to have excellent characteristics such as closed cellular characteristic. Of 0.008 g/cm³, density of 21 Kg/m³, compressive strength coefficient of 2.10×10⁻² and maximum expansion shrinkage of 0.1%. 

What we claim is: .[.1. An expanded article of an olefin polymer comprising an expanded product of an olefin polymer containing at least one compound, which imports little shrinkage to said expanded article after expansion selected from the group consisting of the compounds represented by the formulas (I), (II) and (III) as set forth below in an amount of 0.1 to 10% by weight based on the weight of said resin and having a closed cellular characteristic value of 0 to 0.5 g/cm³, a bulk density of 10 to 200 kg/m³ and a compressive strength coefficient of 2.15×10⁻³ to 2.89×10⁻² : ##STR8## wherein R₁ is an alkyl group having 10 to 24 carbon atoms, X and X' each hydrogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted or a substituent selected from the group consisting of --(CH₂)_(n) NH₂ wherein n is an integer of 1 to 22, ##STR9## wherein R₅ is an alkyl having 1 to 24 carbon atoms, --(R₄ O)_(m) H wherein R₄ is an alkylene group having 1 to 5 carbon atoms and m an integer of 1 to 10, ##STR10## wherein R₅ is an alkyl having 1 to 24 carbon atoms, ##STR11## wherein n is an integer of 1 to 22 and A is hydrogen atom or ##STR12## wherein A' is hydrogen atom or ##STR13## wherein R₂ is an alkyl group having 9 to 23 carbon atoms, Y and Y' each hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent of the formula --(R₄ O)_(m) A₂ wherein A₂ is hydrogen atom, an alkyl having 1 to 24 carbon atoms or acyl having 10 to 24 carbon atoms; ##STR14## wherein [R₃ ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer l, which may be the same or different, each having 9 to 23 carbon atoms, R₄ an alkylene group having 1 to 5 carbon atoms, k an integer of 0 to 7, 1 an integer of 2 to 8 and Z a l-valent residue of l-valent polyhydric alcohol from which l hydroxyl groups are eliminated..]..
 2. An expanded article according to claim 1, wherein the .[.polyolefin resin is a.]. olefin polymer is a polyethylene resin or an ethylenevinyl acetate copolymer resin. .[.3. A process for expanding an olefin polymer, which comprises incorporating at least one compound, which imparts little shrinkage to said expanded polymer after expansion, selected from the group consisting of the compounds of the formulas (I), (II) and (III) as set forth below in a thermoplastic synthetic resin in an amount of 0.1 to 10% by weight based on the weight of said resin together with a blowing agent under the condition maintained at a temperature in the range from about 15° to 300° C. to form an expandable resin composition and then allowing said resin composition to expand utilizing the expanding force of the blowing agent contained therein: ##STR15## wherein R₁ is an alkyl group having 10 to 24 carbon atoms, X and X' each hydrogen atom, an alkyl group having 1 to 24 carbon atoms which may be substituted or a substituent selected from the group consisting of --(CH₂)_(n) NH₂ wherein n is an integer of 1 to 22, ##STR16## wherein R₅ is an alkyl having 1 to 24 carbon atoms, --(R₄ O)_(m) H wherein R₄ is an alkylene group having 1 to 5 carbon atoms and m is an integer of 1 to 10, ##STR17## wherein R₅ is an alkyl having 1 to 24 carbon atoms, ##STR18## wherein n is an integer of 1 to 22 and A is hydrogen atom or ##STR19## wherein A' is hydrogen atom or ##STR20## wherein R₂ is an alkyl group having 9 to 23 carbon atoms, Y and Y' each hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent of the formula --(R₄ O)_(m) A₂ wherein A₂ is hydrogen atom, an alkyl having 1 to 24 carbon atoms or acyl having 10 to 24 carbon atoms; ##STR21## wherein [R₃ ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer l, which may be the same or different, each having 9 to 23 carbon atoms, R₄ an alkylene group having 1 to 5 carbon atoms, k an integer of 0 to 7, l an integer of 2 to 8 and Z a l-valent residue of l-valent polyhydric alcohol from which l hydroxyl groups are eliminated..].
 4. A process according to claim .[.3,.]. .Iadd.8 .Iaddend.wherein the olefin polymer is cross-linked.
 5. A process according to claim .[.3,.]. .Iadd.8 .Iaddend.wherein the olefin polymer is a polyethylene resin, an ethylene-vinyl acetate copolymer resin, or a polypropylene resin.
 6. A process according to any of claims .[.3.]. .Iadd.8 .Iaddend.to 5, wherein the polymer composition is expanded by extrusion foaming by means of an extruder. .Iadd.7. An expanded article of an olefin polymer composition comprising an olefin polymer and at least one compound, which reduces shrinkage of said expanded article after expansion, selected from the group consisting of the amide or complete ester compounds represented by the formula (II) or (III), respectively, as set forth below in an amount of 0.1 to 10 percent by weight based on the weight of said olefin polymer and having a closed cellular characteristic value of 0 to 0.5 g/cm³, a bulk density of 10 to 200 kg/m³ and a compressive strength coefficient of 2.15×10⁻³ to 2.89×10⁻² : ##STR22##.Iaddend. wherein R₂ is an alkyl group having 9 to 23 carbon atoms, Y and Y' each is a hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent of the formula --(R₄ O)_(m) A₂ wherein R₄ is an alkylene group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and A₂ is hydrogen atom, an alkyl having 1 to 24 carbon atoms or acyl having 10 to 24 carbon atoms; ##STR23## wherein [R₃ ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer l, which may be the same or different, each having 9 to 23 carbon atoms, R₄ is an alkylene group having 1 to 5 carbon atoms, k is an integer of 0 to 7, l is an integer of 2 to 8 and Z is an l-valent residue of an l-valent polyhydric alcohol of the formula Z(OH)_(l) from which l hydroxyl groups are eliminated; said expanded article having been prepared by the use of a volatile organic blowing agent. .Iadd.8. A process for expanding an olefin polymer, which comprises incorporating at least one compound, which reduces shrinkage of the resulting expanded polymer after expansion, selected from the group consisting of the amide or complete ester compounds of the formula (II) or (III), respectively, as set forth below into the olefin polymer to be expanded in an amount of 0.1 to 10 percent by weight based on the weight of said olfein polymer together with a volatile organic blowing agent under the condition maintained at a temperature in the range of from about 15° to 300° C. to form an expandable resin composition and then allowing said expandable resin composition to expand utilizing the expanding force of the blowing agent contained therein: ##STR24##.Iaddend. wherein R₂ is an alkyl group having 9 to 23 carbon atoms, Y and Y' each is a hydrogen atom, an alkyl having 1 to 24 carbon atoms, an acyl having 10 to 24 carbon atoms or a substituent of the formula --(R₄ O)_(m) A₂ wherein R₄ is an alkylene group having 1 to 5 carbon atoms, m is an integer of 1 to 10, and A₂ is hydrogen atom, an alkyl having 1 to 24 carbon atoms or acyl having 10 to 24 carbon atoms; ##STR25## wherein [R₃ ] means plural alkyl or hydroxyalkyl groups corresponding in number to the integer l, which may be the same or different, each having 9 to 23 carbon atoms, R₄ is an alkylene group having 1 to 5 carbon atoms, k is an integer of 0 to 7, l is an integer of 2 to 8 and Z is an l-valent residue of an l-valent polyhydric alcohol of the formula Z(OH)_(l) from which l hydroxyl groups are eliminated. 